Curriculum research on Sustainable Development Education in Chinese Higher Education -- Education for SD, SD for Education

(1)

HAL Id: tel-03276111

https://tel.archives-ouvertes.fr/tel-03276111

Submitted on 1 Jul 2021

HAL is a multi-disciplinary open access archive for the deposit and dissemination of sci-entific research documents, whether they are pub-lished or not. The documents may come from teaching and research institutions in France or abroad, or from public or private research centers.

L’archive ouverte pluridisciplinaire HAL, est destinée au dépôt et à la diffusion de documents scientifiques de niveau recherche, publiés ou non, émanant des établissements d’enseignement et de recherche français ou étrangers, des laboratoires publics ou privés.

Curriculum research on Sustainable Development

Education in Chinese Higher Education – Education for

SD, SD for Education

Tongzhen Zhu

To cite this version:

(2)

Laser-induced Nucleation in a

Coaxial Microfluidic Mixer

Thèse de doctorat de l'Université Paris-Saclay

École Normale Supérieure Paris-Saclay

École doctorale n°573 Interfaces : approches interdisciplinaires,

fondements, applications et innovation (Interfaces)

Spécialité de doctorat : Chimie

Thèse présentée et soutenue à Cachan, le 13 Juin 2019, par

Zhengyu Zhang

Composition du Jury :

Président

Alain Ibanez

Directeur de recherche, CNRS (– Institut Néel) Rapporteur Yong Chen

Directeur de recherche, Ecole Normale Supérieure (– UMR 8640) Rapporteur Stéphane Veesler

Directeur de recherche, CNRS (CINaM) Examinateur Sladjana Novakovic

Associate Professor, Vinča Institute of Nuclear Sciences Examinateur David Carrière

Directeur de recherche, CEA (– NIMBE) Examinateur Robert B. Pansu

Directeur de recherche, ENS Paris-Saclay (– PPSM) Directeur de thèse Anne Spasojević - de Biré

Professeure, CentraleSupélec (– SPMS) Co-Directeur de thèse

(3)

(4)

LASER-INDUCED NUCLEATION IN A COAXIAL MICROFLUIDIC MIXER

DISSERTATION

Submitted to the École Doctorale Interfaces of the Université Paris-Saclay in Partial Fulfilment of the Requirements for the Degree of

DOCTOR OF PHILOSOPHY in Chemistry

at

École Normale Supérieure Paris-Saclay by

Zhengyu Zhang

Supervised by Dr. Robert B. Pansu Prof. Anne Spasojević - de Biré

(5)

(6)

Acknowledgement

More than 8200 kilometres had I flied from Beijing to Paris on September 15, 2015. I can still see that day vividly. My mother saw me off at the Beijing International Airport. It was a long, noisy, and freezing flight. I drank much wine and covered my numb body with my father’s coat. Six o’clock in the morning, Director Robert Pansu was waiting at the Aeroport de Charles de Gaulle. That was the first time I took a plane, the first time I stepped on the land of another country, and the first time Director Pansu and I met in person, although we had had video meetings discussing my master study and my forthcoming PhD. He gave me a quick tour of Paris: l’École Normale Supérieure, la Société Chimique de France…, after which we arrived at l’ENS-Cachan. He introduced me to the lab of PPSM and then drove me to the bank, my dorm, and the supermarket. He took care of a new student like a father would. That gave me the first impression of France: warm, kind, and caring. Yet, on the very next day I was hopelessly lost on the RER B (which reflects another aspect of France) for a meeting with Prof. Anne Spasojević - de Biré.

It was Prof. Spasojević - de Biré who recruited me from Beijing, at which time she was the Dean of the École Centrale de Pékin, and I was in the last year of my master studies on rapid solidification of laser melting deposited titanium in the same university. Looking for a PhD position, I was fascinated by her research on laser-induced nucleation and the polymorphism control by laser polarisation. She accepted my application and arranged several meetings on our campus. I would not pretend that I was not shocked when I first saw her in a wheelchair but then quickly amused, because she ran faster than I through flocks of students, once even raced joyfully with a food delivery guy. Yet, it was not for her driving skills that she was famous among Centralians in Beijing, but for her strictness in teaching. Indeed, she has always been kind to me, letting me pay attention to the cultural gap between France and China, drag me back to the original research plan, explaining the knowledge that I should have learnt before, and sometimes testing me.

(7)

fortunately blessed by my research supervisors: Robert and Anne. Professionally, they are always ready to help with the experiment, to answer questions, including stupid ones, and to have discussions. Personally, they have been taking good care of me, helping me fit in the lab and the French society. They are not only my research advisors, but more like my family in France.

I am amazed on a daily basis by Robert’s scope of knowledge and depth of thinking both in and out our field. From him, I have realised that being a scholar is not only about doing experiment and solving equations, but also a way of behaviour, of manner, of language, and of being professional. This can only be learnt through observations: we have been doing experiment together, analysing data together, solving equations together, having lunch together, and attending conferences together. These have been valuable opportunities for me to observe like what a real scientist should be. I treasure this experience as the most important training from my PhD.

I am also amazed on the same daily basis by Anne’s skills, diligence, and strictness. She emphasises on the way of thinking. She has been updating a database of NPLIN related papers filled with the tested compounds, laser types, experimental parameters, results, and proposed mechanisms. She teaches me to rapidly dig pertinent information from literature and to compare with our results. Not only does she work day and night, but also with strictness and efficiency. She urges me to pay attention to details and to timing, for experiments, for writing, and for presentations. She pointed out the smallest flaws in my manuscript, word by word, table to table, figure to figure. I really appreciate that. She is the strongest person I ever know and will always be my inspiration.

(8)

in this thesis could have been accomplished if there had not been him.

Many different techniques were involved in our research. I must also extend a huge thank to our collaborators, colleagues, fellow and former students who contributed to this work, notably: Valérie Génot developed the microfluidic device and the first Comsol model; Director Stéphane Veesler is the parrain de thèse, who travelled from Marseille to Paris to check the progress of the thesis at the midterm and gave me advices; Bi Ran measured the solubility of DBDCS, the mixing properties of the solvents, and anti-solvent focusing of Pastis; Prof. Thomas Rodet extracted the fastest FLIM video from our data; Dr. Wenjing Li taught me how to use the NPLIN setup in SPMS; Prof. Soo Young Park’s team synthesised DBDCS and measured its melting point and melting enthalpy; Director Isabelle Leray and Dr. Naresh Kumar synthesised Calix-cousulf; Dr. Javier Perez, Dr. Mehdi Zeghal, Dr. Guillaume Tresset, and Prof. Brigitte Pansu organised a SAXS experiment at the Synchrotron SOLEIL; Evgeny Turbin, Dr. Yury Prokazov, and Dr. Werner Zuschratter have developed and have been maintaining the FLIM detector; Philippe Scouflaire has built and has been maintaining the NPLIN setup in SPMS; Dr. Vu-Long Tran and Dr. Yuanyuan Liao are the first users of the microfluidic device; Dr. Bertrand Clair and Dr. Aziza IKNI are the first users of the NPLIN setup in SPMS; Nada Bošnjaković-Pavlović is currently doing experiments with the NPLIN setup in SPMS; Arnaud Brosseau is the engineer maintaining the spectroscopy room of PPSM; Jean-Pierre Lefèvre is the engineer for the microfluidic room of IDA; Dr. Rasta Ghasemi is the engineer maintaining the SEM of IDA. Thank you all for your help with our research.

It goes without saying that our research would have gone nowhere without the financial support. I am thankful to the Laboratoire Photophysique et Photochimie Supramoléculaires et

Macromoléculaires (PPSM), to the Laboratoire Structures Propriétés, Modélisation des Solides (SPMS), to the Institut d'ALEMBERT, to the ENS Paris-Saclay, to CentraleSupelec, to

(9)

I would like to also thank my alma mater, Gansu University of Technology, for giving me strict engineering training. This year is her centennial anniversary. I wish her a happy birthday. I am equally thankful to Beijing University of Aeronautics and Astronautics (BUAA), to Prof. Huaming Wang and Dr. Haibo Tang, and to the National Engineering Laboratory of

Additive Manufacturing for Large Metallic Components. BUAA opened my door from

engineering to academics, from China to France. I have been benefiting day-to-day during my PhD from the training in BUAA: thermodynamics, physical metallurgy, physical chemistry,

mass, heat, and momentum transfer in materials processing, XRD, SEM, DSC, DTA, and so on.

There are not enough words in my English vocabulary to express how much I am grateful to my parents. Not only did they support me through the ups and downs, but it was their education, which cultivated my interest and belief in science. They came to France to support me when I was overwhelmed by the manuscript while my wife was about to give birth. They have done more than enough.

Some special thanks are given to my DD (dear daughter), Xingxian, for her kicking, laughing, crying, vomiting, hiccupping, and pooping, alongside my writing the manuscript. Considering your nine months in the uterus, you accompanied nearly half of my PhD. Thank you for being a lovable rascal. You have my unconditional love, but you need to work hard to gain my respect. I cannot wait to see you become a strong, brave, independent woman.

(10)

To my wife

Weixi Wang Zhang

who gives me the best accompany and solace

(11)

Abstract

Crystallisation is one of the elementary operations of chemical engineering. Materials are extracted by crystallisation and purified by recrystallisation. But crystal nucleation remains a mystery, and the classical nucleation theory has been undermined by numerous experimental evidences. We have built a microfluidic precipitation device by mixing solvents to produce and continuously observe the birth of a large number of crystals. The molecule chosen for the study is DBDCS, which is fluorescent in solid state (aggregates, crystals, …), but not in solution. Its nuclei will thus be the first luminous object in the mixture.

We have calculated the thermodynamics of the ternary mixture of water (1)-1,4-dioxane (2)-DBDCS (3) from what is known for the binary mixture of 1-2 and the solubility curve of 3 in 1-2, using a two-body-three-body interaction model. From that we have estimated the diffusion coefficients for Comsol simulation. The thermodynamics of the ternary mixtures hypothesised a liquid phase of 3.

A parametric sweep of the microfluidic parameters was carried out. Three types of spontaneous phase transitions from liquid have been recorded: i) nano-particles; ii) droplets; iii) crystals. By plotting the observations as a function of the average composition of the mixture, a working phase diagram of 1-2-3 in the microfluidic system has been established. Droplets prevail on the phase diagram. The volume fraction of the droplets obeys the lever rule of phase separation to a supersaturated solution and a nearly pure liquid phase of DBDCS (3). The liquid-liquid phase separation requires a strong supersaturation following the diffusion of water (1). The study of the solubility of 3 in 1-2 shows that the chemical potential of DBDCS (3) in water (1) is 17.4 RT higher than that in 1,4-dioxane (2). The diffusion of 1 in 2 induces the formation of an energy barrier that repels and concentrates 3 towards the flow centre. Numerical simulation shows that the supersaturation ratio at the flow centre where the liquid-liquid phase separation occurs is beyond 50 and reaches up to 106_{order of magintue. The product of this}

(12)

of the same size.

As the fraction of 2 increases in the anti-solvent, the potential barrier starts to be outweighed by the configurational entropy of mixing. This is shown by the distribution of the fluorescence of the molecules (𝑦𝑖𝑒𝑙𝑑 < 10−4_{). About five seconds out from the injection}

nozzle, the formation and growth of crystals is observed. The numerical simulation indicates that for crystallisation the supersaturation ratio does not exceed 3.5. Rapid imaging and fluorescence lifetime imaging allow the crystals to be observed one by one. Three different polymorphs are identifiable by fluorescence lifetime: the green and the blue phases already reported, and a short-lived phase. The growth rates are widely dispersed, making it difficult to locate and to observe spontaneous nucleation.

(13)

Résumé

La cristallisation est une des opérations élémentaires du génie chimique. Les matières produites sont extraites par cristallisation et purifiées par recristallisation. Mais la nucléation du cristal reste un mystère et la théorie classique de la nucléation est battue en brèche par de nombreuses données expérimentales. Nous avons construit un dispositif microfluidique de précipitation par mélange de solvants pour produire de manière continue et observer la formation d’un grand nombre de cristaux. La molécule étudiée est le DBDCS dont les cristaux sont fluorescents mais pas la molécule. Le germe sera ainsi le premier objet lumineux du mélange.

Nous avons calculé la thermodynamique du mélange ternaire DBDCS-1,4-dioxane-eau à partir de ce qui est connu pour le mélange 1,4-dioxane-eau et de la courbe de solubilité du DBDCS dans 1,4-dioxane-eau, dans le cadre du modèle H3_{M. Ceci nous a permis de fournir a}

Comsol les valeurs des coefficients de diffusion du mélange ternaire. La thermodynamique des

mélange ternaires postule une phase liquide du DBDCS.

Nous observons cette phase dans une expérience de précipitation après 1ms de mélange. La mesure du volume de cette phase liquide confirme qu’elle est pratiquement pure. L’apparition de cette phase liquide nécessite une forte sursaturation. Celle-ci fait suite à la diffusion de l’eau qui repousse et concentre le DBDCS au centre du dispositif. L’étude du temps mis à atteindre la concentration critique en fonction de la concentration initiale en DBDCS dans le flux central permet d’obtenir une valeur de 50 à 70 fois la saturation pour la concentration critique d’apparition de la phase liquide DBDCS. Le produit de cette décomposition liquide-liquide est un nuage de gouttelettes sub-micrométriques. Mais le gradient de potentiel chimique peut, dans certaines conditions, regrouper ces nano-gouttes en un chapelet de gouttes micrométriques de même taille.

(14)

de la fluorescence résiduelle des molécules (rendement<10-4_{). Sur des temps de l’ordre de 5s,}

on observe la formation et la croissance de cristaux dans un mélange localement homogène. La simulation numérique indique que dans ces conditions la sursaturation relative ne dépasse pas 3,5. L’imagerie rapide et la fluorescence permettent d’observer les cristaux un par un. Trois polymorphes différents sont identifiables par leur durée de vie : les phases vertes et bleues déjà observées et une phase de courte durée de vie. Ces cristaux présentent une vitesse de croissance moyenne proportionnelle à la concentration locale.

En focalisant un laser sur les nuages de nano-gouttes, on observe un effet de pince optique capable de rassembler ces gouttes. En focalisant ce laser dans la zone de super-saturation maximale dans des conditions de nucléation spontanée, on observe une multiplication du nombre de cristaux formés d’un facteur cinq. Nous sommes en présence d’une nucléation induite par laser. Ces cristaux présentent la même vitesse de croissance, la même distribution en nombre des polymorphes, que les cristaux obtenus spontanément. Cette nucléation induite par laser est donc très douce et induit un changement minimal du mécanisme de la nucléation. Un effet de pince optique qui concentre localement les précurseurs du germe et augment transitoirement la sursaturation pourrait avoir cet effet.

(15)

Table of nomenclatures

Notation Definition Unit

Latin letters

a, b, c lattice length parameter m

A

area m2

m

A

molar surface area m2_∙mol-1

x

B

accumulative crystal birth rate from nozzle to x μm s-1 2

1

x x

B sectional crystal birth rate during x1~x2μm from

nozzle s

-1∙m-1 c , p

subscripts “c” and “p” denote central and peripheral flows, respectively

d

distance m

L

d

distance from nozzle to the induction laser focal point m

N

d

distance between two successive nucleation events in

microflow m

P

d

phase transition starting distance from nozzle m

D

diameter m

F

i

D intrinsic diffusion coefficient of species i m2_∙s-1 F

ij

D mutual diffusion coefficient of species i and j m2_∙s-1

D diffusion coefficient in infinite dilute solution m2_∙s-1 *

D self-diffusion coefficient m2_∙s-1

f hydrodynamic factor of maximum central flow radius 1

rep

f laser pulse repetition rate Hz

F

force N

A

g

crystal area growth rate m2_∙s-1

L

g

crystal linear growth rate m∙s-1

m

G

molar Gibbs energy J∙mol-1

L v

G volume Gibbs energy of liquid phase J∙m-3

s v

G volume Gibbs energy of solid phase J∙m-3

L

sGv

 volume Gibbs energy change from liquid to solid J∙m-3 N

G



Gibbs energy change of a nucleus J

* N

G

 nucleation energy barrier

melt

H

v



volume melting enthalpy J∙m-3

r

H

m



molar enthalpy of a reaction J∙mol-1

I

optical intensity W∙m-2

I

identity tensor, matrix

j flux in moving coordinate system kg∙m-2_∙s-1

J

flux in fixed coordinate system kg∙m-2_∙s-1

k

rate constant

FRET

(20)

F

k

fluorescence decay rate constant

IC

k

rate constants of internal conversion

ISC

k

rate constants of intersystem crossing

ISOM

k

rate constants of isomerisation

N

K

nucleation rate constant

Q

k quenching rate constant

c

l

concentration entrance length m

h

l

hydrodynamic entrance length m

c

L

length of a crystal m

i

M

molar mass of species i kg∙mol-1

n

M

mean molar mass kg∙mol-1

n

amount mol

D

n

refractive index 1

N

number of particles 1

*

N number of nuclei per unit volume m-3

ab

N

number of photons absorbed 1

em

N

number of photons emitted 1

H

N

heterogeneous nucleation rate m-3_∙s-1

L

N

Laser-induced nucleation rate m-3_∙s-1

S

N

spontaneous nucleation rate m-3_∙s-1

p

_probability ₁

avg

P laser average power W

Pe

Péclet number 1

peak

P _{laser peak power} _W

Q flow rate m3_∙s-1

A

Q

activation energy J∙mol-1

c

Q

central flow rate m3_∙s-1

mix

Q



loss of flow rate after mixing of solvents m3_∙s-1 p

Q peripheral flow rate m3_∙s-1

r

radius m

r critical radius m

3

r radius of liquid DBDCS molecules m

c,max

r maximum radius of a jet m

drop

r _{radius of droplet} _m

o

r

radius of a cylindrical tube before it breaks in to

droplets m

channel

R

radius of a microfluidic channel m

Re

Reynolds number 1

FRET

(21)

m

R

molar refractivity m3_∙mol-1

S

singlet state

r

S

m



molar entropy change of a reaction J∙mol-1_∙K-1

t time s

I

t

induction period s

N

t

nucleation event time interval s

T

triplet state

T

temperature K T _{Transpose of a matrix} melt

T

melting point K

T



supercooling K

v

velocity field m∙s-1

v

advective velocity of a laminar flow m∙s-1

effective

v

effective velocity of a laminar flow m∙s-1

max

v

maximum flow velocity of a laminar flow m∙s-1

F

v diffusive velocity m∙s-1

F r

v

average antisolvent focusing velocity of a solute m∙s-1

V

volume m3

m

V

molar volume m3_∙mol-1

mix

V

m



excess molar mixing volume m3_∙mol-1

w

focused laser beam radius m

i

x

amount fraction of species i 1

s

x

amount fraction solubility 1

b

i j

x amount fraction binodal decomposition limit of

species i in j 1

s

i j

x amount fraction solubility of species i in j 1

spin

i j

x amount fraction spinodal decomposition limit of

species i in j 1

, ,

x y z

_{Cartesian coordinates}

, ,

x r



_{horizontal cylindrical coordinates} Greek letters

  

，， _{lattice angle parameter} _°



supersaturation ratio 1



_{surface tension} _N∙m-1_{, J∙m}-2

sL



interfacial free energy between solid and liquid phase N∙m-1_{, J∙m}-2

i



activity coefficient of species i



Hamiltonian operator

2

 Laplace operator



_{kinetic viscosity} _m2_∙s-1

(22)



period of in the Plateau–Rayleigh instability m

em



emission wavelength m



_{chemical potential} J∙mol-1



dynamic viscosity Pa·s



frequency Hz



_{mass concentration} _kg∙m-3

D



mass density kg∙m-3

b



mass concentration binodal decomposition limit kg∙m-3 b

i j



mass concentration binodal decomposition of species

i in j kg∙m

-3

s



solubility in mass concentration kg∙m-3

s

i j



mass concentration solubility of species i in j kg∙m-3 spin



mass concentration spinodal decomposition limit kg∙m-3 spin

i j



mass concentration spinodal decomposition limit of

species i in j kg∙m -3



 supersaturation kg∙m-3



sum F



fluorescence lifetime s p



laser pulse width s

i



volume fraction of species i 1

o

i



volume fraction of species i without considering the

solute 1

F



quantum yield

Other



inner product operator



outer product operator



integral



partial derivative

(23)

List of acronyms and abbreviations

ABS acrylonitrile butadiene styrene

ac alternating current

AIE aggregation-induced emission

ATR-FTIR attenuated total reflectance Fourier-transform infrared spectroscopy

BF bright field

CCD charge-coupled device

CL circular left-handed

CMOS complementary metal–oxide–semiconductor CNT classical nucleation theory

CP crossed polarisers

CR circular right-handed

CW continue wavelength

DBDCS (2Z,2'Z)-2,2'-(1,4-phenylene)bis(3-(4-butoxyphenyl) acrylonitrile)

dc direct current

DLS dynamic light scattering

DSC differential scanning calorimetry

DVP divinyl benzene

EF electric field

ENS Paris-Saclay École Normale Supérieure Paris-Saclay FBRM beam reflectance measurement

FEP fluorinated ethylene propylene

FLIM fluorescence lifetime imaging microscopy FRET Förster resonant energy transfer

fs femtosecond

HEWL hen-egg white lysozyme

IC internal conversion

ID inside diameter

IR infrared

ISC intersystem crossing

ISOM isomerisation

LLPS liquid-liquid phase separation

NA numerical aperture

NIR near-infrared

NPLIN non-photochemical laser-induced nucleation

OD optic density

OD outside diameter

OM optical microscopy

PCA principal component analysis

PDMS polydimethylsiloxane

PEEK polyether ether ketone

PNC pre-nucleation cluster

POTS 1H,1H,2H,2H-perfluorooctyltriethoxysilane

PPSM Laboratoire de Photophysique et Photochimie Supramoléculaires et Macromoléculaires

PVM particle vision and measurement

ROI region of interest

SAXS small angle X-ray scattering SEM scanning electron microscopy

SPMS Laboratoire Structures Propriétés et Modélisation des Solides ssNMR solid-state nuclear magnetic resonance

SVA solvent vapor annealing

(24)

TEM transmission electron microscopy TICT twisted intramolecular charge transfer

TPE tetraphenylethylene

TSCSPC time- and space- correlated single photon counting TST two-step nucleation theory

UV ultraviolet

vr vibrational relaxation

WF wide-field

WD working distance

(25)

Table of physical constants

Quantity Symbol Value Unit

Elementary charge

e

1.602 176 487(40) × 10−19 C

Faraday constant

N

_A



e

F

96 485.3399(24) C∙mol-1

Boltzmann constant

R N

/

_A

k

_B 1.380 6504(24) × 10−23 J∙K-1

Avogadro constant

N

A 6.022 141 79(30) × 1023 mol-1

(26)

List of figures

Figure 1.1. Chronology of scientists and their contributions towards understanding

nucleation. (Adapted from [Kathmann, 2005])... 8

Figure 1.2. Sketch of the Gibbs energy gain



G

_N

as a function of the crystalline

nucleus size r. (Adapted from [Sosso, 2016]) ... 12

Figure 1.3. Schematic comparison of the Gibbs energy gain



G

_N

and the structural

change in terms of the cluster size r (Adapted from [Sosso, 2016]) ... 15

Figure 1.4. Schematic definition of NPLIN used in this manuscript. ... 18

Figure 1.5. Growth of the papers on NPLIN according to our extended definition. . . 18

Figure 1.6. Distribution of NPLIN papers according to the compounds studied. ... 19

Figure 1.7. Some key-figures of NPLIN setups.. ... 20

Figure 1.8. Schematic representation of NPLIN sample-holders. ... 21

Figure 1.9. The movement of the flow around a drop of DVB in a gradient of water

(channel wall) and ethanol (channel centre). (Adapted from [Hajian, 2015]) ... 25

Figure 1.10. Schematic representation of the electron in the ground or excited state. 26

Figure 1.11. Schematic energy levels in atoms, molecules, and semiconductors.

(Adapted from [Douglas, 2013])... 27

Figure 1.12. Simple Jablonski diagram illustrating the primary deactivation processes

occurring upon excitation. Electronic levels are represented by heavy lines. (Adapted

from [Douglas, 2013]) ... 28

Figure 1.13. Effect of defects in a fluorescent crystal. ... 32

Figure 1.14. Molecular structure of DBDCS. ... 36

Figure 1.15. Schematic illustration for the preparation of DBDCS using a reactive

inkjet printing method. (Adapted from [Jeon, 2015]) ... 36

Figure 1.16. IR spectral change in DBDCS film due to the UV irradiation or heating.

The asterisk indicates the band of CO

2

. (Adapted from [Fujimori, 2016]) ... 37

Figure 1.17. Photo of DBDCS crystals. (Adapted from [Yoon, 2010]) ... 38

Figure 1.18. Fluorescence microscope images of DBDCS spots after 24 h at different

temperatures on glass and PDMS films (𝜆ex 330~385 nm). (Adapted from [Jeon,

2015]) ... 38

Figure 1.19. The absorption and fluorescence spectra of DBDCS in CHCl

3

. (Adapted

(27)

Figure 2.4. Parameters of the coaxial microfluidic mixer. ... 53

Figure 2.5. Clogging of the borosilicate syringe after a long time of experiment. A:

clogging by caesium acetate in THF-water microflow; B: clogging by DBDCS

precipitation in water (1)-1,4-dioxane (2). ... 54

Figure 2.6. Loss of flow rate after mixing coflow of water (1)-1,4-dioxane (2) and of

water (1)-THF (2) calculated using equation 2.9 in terms of volume fractions. ... 56

Figure 2.7. Central flow jet shape after injection nozzle. ... 58

Figure 2.8. Central flow maximum radius as function of central/peripheral flow ratio.

Data is well described by equation (2.14). ... 59

Figure 2.9. Design from the supporter for the microfluidic capillaries. ... 62

Figure 2.10. Assembled diffusive coaxial microflow antisolvent precipitation system.

... 63

Figure 2.11. Schematic illustration of the laser and microscopy setup for microfluidic

NPLIN and FLIM ... 64

Figure 2.12. Laser and microscope setup for microfluidic NPLIN and FLIM mounted

with the microfluidic system. ... 67

Figure 2.13. Parametric matrix of the experimental inputs and outputs for water

(1)-1,4-dioxane (2)-DBDCS (3) system. * denotes supersaturated mother solution. ... 68

Figure 2.14. Calliper fixed on the microscope stage to measure distance in the

microflow. ... 69

Figure 2.15. Adjustable microscope stage movement blocker (in the red circle). ... 70

Figure 2.16. The microfluidic system mounted on X-ray line SWING of synchrotron

Soleil. ... 71

Figure 3.1. Molar excess mixing volume of water (1)-1,4-dioxane (2) binary mixture

at 298.15 𝐾 [Aminabhavi, 1995]... 77

Figure 3.2. Estimation and experimental values of the mixing properties of water

(1)-1,4-dioxane (2) binary system at 298.15 𝐾. ... 80

Figure 3.3. Stability of ideal solutions.

mixGm

of ideal binary (A) and ternary (B)

(28)

Figure 3.14. Thermodynamic stability of the binary system of DBDCS and

1,4-dioxane at 298.15 K. ... 118

Figure 3.15. Thermodynamic stability of the binary system of DBDCS and water at

298.15 K. ... 120

Figure 3.16. Stability of water (1)-1,4-dioxane (2)-DBDCS (3) ternary mixture... 122

Figure 3.17. A calculated ternary phase diagram of water (1)-1,4-dioxane (2)-DBDCS

(3).. ... 124

Figure 3.18. Zoom in of the Gibbs energy of DBDCS in water (1)-1,4-dioxane (2)

mixture near the soluble domain. ... 125

Figure 4.1. Axisymmetric geometry of the simulation domain of the reactive part of

the coaxial microflow mixer. ... 130

Figure 4.2. An example of the parametric sweep simulation:



_3c

= ,

0 Q =

_c

370 nl min

,

1p 100%



=

,

Q =_p 1μl min

... 134

Figure 4.3. Comparison of the OM images and Comsol simulation of the refractive

index

n of a parametric sweep of a central flow of 1,4-dioxane into a peripheral flow

_D

of water. The microfluidic parameters are marked on the small OM images. ... 135

Figure 4.4. Comparison of the Comsol simulation (■), theoretical calculation (line)

and the experimental measurement (▲) of the maximum central jet

r_c,max

as a function

of flow ratio... 136

Figure 4.5. Comsol simulation of the development of a laminar flow of a Poiseuille

velocity profile along its radius... 137

Figure 4.6. Parametric sweep simulation of flow velocity profiles along tube centre

(top) and its gradient (bottom) on the flow direction. The hydrodynamic entrance

length

l is 200 µm. ... 138

_h

Figure 4.7. Comsol simulation of the development of a homogeneous concentration..

... 139

Figure 4.8. Parametric sweep simulation of 1,4-dioxane mass concentration along

flow centre (top) and its gradient (bottom) on the flow direction. This reflects the

concentration entrance length

l of the flow. ... 140

_c

Figure 4.9. Simulation of DBDCS diffusion in a field of solvent composition... 141

Figure 4.10. Simulation of DBDCS diffusion in a field of solvent composition. ... 143

Figure 5.1. Typical phenomena observed in the coaxial microfluidic mixer with water

(1)-1,4-dioxane (2)-DBDCS (3) system. ... 147

Figure 5.2. A whole image of the demixing. ... 149

Figure 5.3. Evidences and simulation for antisolvent focusing of DBDCS. ... 150

Figure 5.4. Working phase diagram of water (1)-1,4-dioxane (2)-DBDCS (3) phase

diagram in the microfluidic mixer measured by a parametric sweep. ... 152

Figure 5.5. Precipitation of a vague line and its disappearance because the diffusion of

solute driven by the anti-solvent composition gradient, frames taken from a video

moving along the flow. ... 154

Figure 5.6. A column of DBDCS nano-particles formed along the flow centre. ... 156

Figure 5.7. By blocking the microfluidic channel, the flow was temporarily stopped,

and the nano-particles were “frozen” in the suspension. ... 156

Figure 5.8. Precipitation of a dark line later dispersed in to a column of nanoparticles,

frames taken from a video along the flow. ... 157

Figure 5.9. In situ OM transmission image (left) and CP image (right) of the

(29)

Figure 5.10. Drying process of a suspension of DBDCS nano-particles collected on a

glass slide. ... 159

Figure 5.11. A~C: post-mortem SEM image of DBDCS nano-particles collected on

copper grid; D~F: bigger objects appeared among nano-particles after 1 month. ... 159

Figure 5.12. Nanoparticles gathered to be droplets. ... 160

Figure 5.13. Droplets along the flow. ... 161

Figure 5.14. Zoom of formation of droplets. A: droplets appeared from the centre of

the microfluidic channel and then grow and merge to a stable size. ... 162

Figure 5.15. Direct breaking of the centre flow by a Plateau–Rayleigh instability. .. 163

Figure 5.16. Frames taken from a video of abnormally large droplet in trapped by

Marangoni effect with t the elapsed time in the video.. ... 164

Figure 5.17. A: abnormally large droplet dragged to the tip by the strong Marangoni

effect and left remanence on the nozzle; B: abnormally large droplet crystallised and

flushed away by the flow. ... 165

Figure 5.18. Crystallisation of trapped abnormally large crystals observed during a

washing. ... 166

Figure 5.19. Inner structure of the trapped abnormally large droplet.. ... 167

Figure 5.20. Post-mortem OM observation of the droplets ... 168

Figure 5.21. Collected dark line of droplets on glass slide. A: suspension in solvents

mixture; B: dried. ... 169

Figure 5.22. Crystallisation of the liquid DBDCS stacked as a pillar along the flow

centre.. ... 169

Figure 5.23. Two-step crystallisation of caesium acetate in the microfluidic mixer. 170

Figure 5.24. By changing only

Q_p

,

d was observed to be fixed at

_P

430 µ𝑚 ... 173

Figure 5.25. Schematic illustration of the movement of DBDCS in the antisolvent

focusing of the coaxial microfluidic mixer. ... 174

Figure 5.26. Dependence of average anti-solvent focusing velocity

F

r

v on microfluidic

input parameters.. ... 178

Figure 5.27. Prediction of slopes as a function of flow ratio. ... 180

Figure 5.28. Dependence of the average anti-solvent focusing velocity of DBDCS on

3c

 in the coaxial mixer of water (1)-1,4-dioxane (2) flows. ... 181

Figure 5.29. Dependence of the average anti-solvent focusing velocity of DBDCS on

1p

 ,

c p

Q

, and

 in the coaxial mixer of water (1)-1,4-dioxane (2) flows. ... 182

3c

Figure 5.30. The chemical potential focusing limit (red) of DBDCS by water

(1)-1,4-dioxane (2) in the working phase diagram of water (1)-1,4-(1)-1,4-dioxane (2)-DBDCS (3) in

coaxial microfluidic mixer. ... 184

Figure 5.31. LLPS and nano-precipitation starting position’s dependence on

microfluidic control parameters. ... 186

Figure 5.32. Dependence of

d on

P

 and

3c

 . ... 187

1p

Figure 5.33. Droplet formation position as a function of

Q ,

_c

 and

_3c

 . ... 188

_{1 p}

Figure 5.34. New prediction of antisolvent focusing velocity and droplet formation

distance with equation (5.4) and (5.5) using fitted parameters. ... 191

Figure 5.35. Size dependence of droplets on

Qp

. ... 192

(30)

water (1)-1,4-dioxane (2)-DBDCS (3). ... 195

Figure 5.39. Total droplet volume fraction is linear with DBDCS total concentration.

Every millilitre of the droplet phase contains 1.2 g DBDCS. ... 196

Figure 5.40. Surface tension of binary mixture of water (1)-1,4-dioxane (2). ... 199

Figure 5.41. Droplets radius as a function of

 and

_{1 p}

r . ... 201

₀

Figure 5.42. Droplet radius measurement vs prediction by Plateau-Rayleigh instability

model... 202

Figure 6.1. Spontaneous crystallisation of DBDCS from water-1,4- dioxane mixture

in the coaxial microfluidic mixer.. ... 208

Figure 6.2. Crystal habit of DBDCS spontaneous crystallisation from water

(1)-1,4-dioxane (2) in the coaxial mixer ... 209

Figure 6.3. Crystal habit of DBDCS spontaneous crystallisation from

water-(THF20-1,4-dioxane80) in the coaxial mixer. ... 210

Figure 6.4. Schematic formation mechanism of the “butterfly” twin crystal habit of

DBDCS in the microflow... 211

Figure 6.5. Drying process of the DBDCS butterfly crystals collected at the end of the

microfluidic channel. ... 212

Figure 6.6. Small crystals grow appeared at the “empty” space. ... 212

Figure 6.7. Heterogeneous DBDCS crystals on the microfluidic channel wall... 213

Figure 6.8. FLIM image of three crystals grown on the wall from a flow of

water-(THF20dioxane80)-DBDCS mixture... 214

Figure 6.9. Fluorescence intensity and lifetime treatment of DBDCS spontaneous

crystals in the microflow of water (1)-1,4-dioxane (2). ... 215

Figure 6.10. A collection of fluorescence decays collected at different position along

the spontaneous crystallisation in the flow ... 217

Figure 6.11. The fluorescence lifetime images collected along the spontaneous

crystallisation in the microflow ... 218

Figure 6.12. Comsol simulation of the volume fraction of water, the solubility, the

mass concentration, and supersaturation of DBDCS in the microflow ... 219

Figure 6.13. The decays collected from different areas on the FLIM map along the

spontaneous crystallisation in the flow ... 220

Figure 6.14. The PCA of the fluorescence decays collected on the FLIM map. ... 221

Figure 6.15. Contribution from the principal components to the fluorescence intensity

in the time trace. ... 222

Figure 6.16. Contribution from the “Oligo” DBDCS and the crystals to the

fluorescence intensity in the two regions of interests along the microflow. ... 223

Figure 6.17. The residuals of the data described by the four components: Microscope,

Molecule, “Oligo” and “CPFluctant”. ... 224

Figure 6.18. The fluorescence intensity (red) and lifetime (blue) signal collected from

the flow centre area. ... 225

Figure 6.19. Fluorescence intensity and lifetime after the correction of the detection

time. ... 226

Figure 6.20. Frames of the fastest FLIM video. ... 227

Figure 6.21. The total number of photons counted per DBDCS crystal versus the

transit time through a virtual line in the flow. ... 228

Figure 6.22. Rotation of crystals in the flow of DBDCS crystals in a mixture of

water-THF in the coaxial microflow.. ... 229

Figure 6.23. Comsol simulation of the mass concentration (solid curve) and

supersaturation (dashed curve) of DBDCS along the flow centre for different

(31)

Figure 6.24. Number distribution of the nucleation event time interval,

t , measured

_N

by FLIM.. ... 233

Figure 6.25. FLIM measurement of the DBDCS crystal area

A distribution and

_c

accumulative birth rate

B_x

along the microflow. ... 234

Figure 6.26. The correlation between the fluorescence lifetime of individual particles

and their size for six positions along the flow. ... 236

Figure 6.27. OM measurement of nucleation rate and growth rate of spontaneous

crystallisation versus distant from injection nozzle (bottom axis) and residence time

(top distance). ... 239

Figure 6.28. OM measurement of nucleation rate and growth rate of spontaneous

crystallisation versus distant from injection nozzle (bottom axis) and residence time

(top distance).. ... 241

Figure 6.29. Summary of all the spontaneous phase transition behaviours observed in

the coaxial microfluidic system. ... 243

Figure 7.1. Laser-induced DBDCS crystals from a mixture of water (1)-1,4-dioxane

(2) in the coaxial microfluidic mixer. ... 249

Figure 7.2. FLIM image of the microfliudic NPLIN in Figure 7.1. ... 250

Figure 7.3. The fluorescence decays of DBDCS molecules with and without the IR

femtosecond laser... 251

Figure 7.4. Spontaneous crystallisation and growth of DBDCS along the coaxial

microfluidic mixer without IR laser. ... 253

Figure 7.5. Growth process of the laser-induced crystals along the microfluidic

channel. ... 254

Figure 7.6. Growth process of the crystals induced with half the full laser power. . 255

Figure 7.7. Comparison the nucleation rate and the growth rate between laser-induced

(red) and spontaneous crystallisation (olive) under the same microfluidic conditions in

the coaxial mixer measured by OM. . ... 258

Figure 7.8. Comparison of the FLIM measurement of the laser-induced nucleation

(red) and spontaneous nucleation (blue) of DBDCS in the coaxial microflow. ... 259

Figure 7.9. The fluorescence lifetime distribution (the curve covering the circles

plotted vertically at the distance from nozzle) of laser-induced (red) and the

spontaneous (blue) DBDCS crystals measured along the coaxial microflow.. ... 261

Figure 7.10. Impact of laser induction position. Laser was turned on at different

distance

d to the nozzle.. ... 262

_L

Figure 7.11. The impact of the laser induction position

d on the laser-induced crystal

_L

birth-rate

B_10mm

. ... 264

Figure 7.12. Impact of IR laser power

P_avg

on induced crystals. Observed 10100 µm

from the nozzle. ... 265

Figure 7.13. Impact of laser average power

Pavg

on laser-induced crystal the birth rate

10mm

B

. ... 266

Figure 7.14. Size of laser-induced crystals decreased with laser average power

P_avg

.

... 267

Figure 7.15. Impact of laser repetition rate

frep

on laser-induced crystals.. ... 269

Figure 7.16. Cross comparison of the impact of laser average power

P_avg

on

laser-induced crystal birth rate

B10mm

at different repetition rate

frep

. ... 270

(32)

from water (1)-1,4-dioxane (2) mixture. ... 271

Figure 7.18. Impact of laser polarisation on the accumulative crystal birth rate

B_10mm

of DBDCS in the coaxial microflow of water (1)-1,4-dioxane (2). ... 272

Figure 7.19. Post-mortem OM image of collected laser-induced crystals on glass

slides. ... 273

Figure 7.20. The effect of the focused femtosecond IR laser on the interface between

the central jet of 1,4-dioxane and the peripheral flow of water. ... 274

Figure 7.21. Impact of focused IR laser on droplet formation... 275

Figure 7.22. A~B: two examples of laser releasing abnormally large droplets from the

droplet trap. C: the process how laser released the trapped droplets.. ... 277

Figure 7.23. By increasing the contrast of the image, it shows laser had induced a dark

line before releasing the suspended large droplet.. ... 278

Figure 7.24. Laser’s effect on the size of the droplets. ... 278

Figure 7.25. Laser induced a dark line in the nano-sized precipitation of DBDCS in

the microflow. ... 280

Figure 7.26. OM transmission image and CP image of laser-induced droplet formation

from amorphous nano-objects and the crystallisation of the droplets later in the

microflow. ... 281

Figure 7.27. Laser-induced explosion dependence on laser average power ... 283

Figure 7.28. Laser-induced explosion dependence on flow velocity... 284

Figure 7.29. Impact of laser induction position on interaction with DBDCS

nano-particles.. ... 285

Figure 7.30. Using the femtosecond IR laser as tweezers to move impurities in pure

water. ... 287

Figure 7.31. A~C: laser-induced explosion, ablation, and bubbles on surface of

absorbing solids; D: capillary wall burnt by long time laser explosion. ... 288

Figure 7.32. Summary of spontaneous phase transition types and the effect of the

focused fs IR laser in the coaxial microfluidic system with some characteristic

parameters of interest are marked on the schemes... 289

Figure 7.33. Microfluidic NPLIN working phase diagram... 291

Figure D.1. Lifetime decay (ns) of “object” produced in the microfluidic device

compared to the literature (black circle). ... 307

Figure D.2. Experimental SAXS spectra of DBDCS crystals in microfluidic device.

... 308

Figure D.3. Theoretical powder X-ray diffraction spectra of DBDCS calculated by

reciprOgraph ... 309

Figure D.4. Extraction of Table S2 from [Yoon, 2010]. The Green and the Blue

phases in ground powder sate are indicated with a coloured border. ... 309

Figure D.5. Schematic illustration of a complete full NPLIN experiment in our

(33)

List of tables

Table 2.1. Parameters of mixing volume functions for binary mixtures of water

(1)-1,4-dioxane (2) and water-THF [Aminabhavi, 1995] ... 55

Table 2.2. Average power of the IR laser on the sample plane of different

polarisations (P: parallel to flow; S: vertical to flow; CL: circular left-handed; CR:

circular right-handed)... 66

Table 2.3. Laser and microscope configuration and type of experiment ... 66

Table 3.1. Basic physical properties of the materials in this thesis at 298.15 𝐾:

dynamic viscosity  , surface tension



, molar surface

A , density

_m



_D

, refractive

index

n , molar refractivity

_D

R , molar mass M and molar volume

_m

V .

m

*

_denotes

calculation of a solute state. ... 76

Table 3.2. Parameters of mixing functions for binary mixtures of H

2

O and

1,4-dioxane[Aminabhavi, 1995] ... 77

Table 3.3. Model constants in the Jouyban-Acree model for water (1)-1,4-dioxane (2)

system [Jouyban, 2007] ... 93

Table 3.4 Recalculation of DBDCS amount fraction solubility, measured by Ran Bi in

mass ratio, in binary system of water (1)-1,4-dioxane (2) ... 93

Table 3.5 Fitting parameters for estimation of

_mixG_m

of water (1)-1,4-dioxane

(2)-DBDCS (3) ternary mixture ... 97

Table 3.6. Curve fitting parameters in Figure 3.8 ... 98

Table 3.7. Curve fitting parameters in Figure 3.6 ... 98

Table 3.8 Curve fitting parameters from solubility in pure solvent ... 99

Table 3.9. Measurement of self- [Holz, 2000] and mutual [Leaist, 2000] diffusion

coefficients of water and 1,4-dioxane at 298.15 𝐾, with

F

12

(34)

Conditions and Figures are given as examples. ... 310

Table D.11. Different conditions and nucleation methods to obtain droplets from our

microfluidic device in the ternary mixture water (1)-1,4-dioxane (2)-DBDCS (3).

Conditions and Figures are given as examples. ... 311

Table P.1. Examples of experiment to be done on DBDCS solvent-antisolvent

(35)

List of appendixes

A.i. Thermodynamic versus kinetic aspect of nucleation ... Appen-1 A.ii. Bibliography description of NPLIN experiment ... Appen-2 A.iii. Experimental techniques for crystallisation observation ... Appen-10 A.iii.i. Classical techniques for crystallisation observation ... Appen-10 A.iii.ii. Techniques for pre-nucleation clusters observation... Appen-11 A.iv. Bibliography of DBDCS characterisation ... Appen-16 A.v. Preliminary test materials ... Appen-18 B.i. Technical details of the microfluidics ... Appen-19 B.i.i. The microfluidic system holder ... Appen-19 B.i.ii. Microfluidic capillaries, connectors, and chambers ... Appen-19 B.i.iii. Pumps system, Harvard Apparatus ... Appen-20 B.ii. Structure of the coaxial microflow ... Appen-20 B.ii.i. Central jet radius... Appen-20 B.ii.ii. Flow entrance length ... Appen-21 B.iii. Assembling the microfluidic system ... Appen-22 B.iii.i. Assembling procedures ... Appen-22 B.iv. Problems related with the microfluidic device ... Appen-27 B.iv.i. Cleanness of the capillaries ... Appen-27 B.iv.ii. Temperature control ... Appen-28 B.iv.iii. Deformation and degradation of the device ... Appen-28 B.iv.iv. Precipitation on the injection nozzle of the central flow ... Appen-29 B.iv.v. Working distance of the objective ... Appen-30 B.iv.vi. Leakage and bubble ... Appen-30 B.iv.vii. Influence of gravity ... Appen-30 B.iv.viii. Flow expansion by the big capillary ... Appen-30 B.v. Technical details of the laser sources and illumination type ... Appen-31 B.v.i. Diascopic illumination for bright field (BF) imaging, KhÖler illumination

typ..… ……….Appen-31 B.v.ii. Episcopic illumination for wide-field fluorescence (ep-fl) imaging and IR focusing: ... Appen-31 B.vi. Technical details of the microscope and optics ... Appen-32 B.vi.i. Microscope ... Appen-32 B.vi.ii. Objective and filters arrangement ... Appen-32 B.vii. Technical details of the sensor and detector ... Appen-33 B.vii.i. CCD camera Retiga R1, QImaging... Appen-33 B.vii.ii. QA–Fluorescence Life time Imaging (FLIM) ... Appen-33 B.viii. Laser power, repetition rate, and laser focal spot intensity profile ... Appen-34 C.i. Thermodynamic activity of water (1)-1,4-dioxane (2) system ... Appen-37 C.ii. Limitation of H3_{M model and Acree-Jouyban equation ... Appen-37}

C.iii. Estimation of the melting point, the solid-liquid phase change enthalpy and

entropy of DBDCS ... Appen-42 C.iv. Recent development on the mutual diffusion coefficient of self-associating species ... Appen-46

(36)

D.ii. Justification of separation of the concentration- and composition- driven diffusion by using the migration in electric field model in Comsol ... Appen-52

E.i. FLIM measurement of spontaneous precipitation of Calix-Cousulf-Cs+2

(37)

(38)

Nucleation is a frontier of chemistry. The classical nucleation theory postulates that the transition state which is at the maximum of the energy barrier on the way to crystallisation is a small crystal. This explains the control of crystallisation by kinetics, the production of various polymorphs, and the existence of an amorphous phase and supersaturated solutions. But there are evidences that contradict this model for not describing the actual crystallisation routes [Karthika, 2016]. Crystal growth and design is still the domain of a knowhow and art.

The control of crystal polymorphism is important in the metal industry for mechanical properties, in the pharmaceutical industry for solubility and bioavailability properties, and in the semiconductor industry for electronic properties.

(39)

an electromagnetic term the Gibbs energy.

Recently, the Laboratory Photophysique & Photochimie Supramoléculaires et

Macromoléculaires (PPSM) UMR 8531 du CNRS, l’ENS Paris-Saclay has developed a

microfluidic device for the observation of fluorescent crystals and precipitates [Tran, 2016]. The polymorphs of the fluorescence molecule can be distinguished by their fluorescence lifetimes. The uphill diffusion of the solute by a repulsion by the anti-solvent is a known concept that is included in the fundamental equations of thermodynamic of ternary mixtures [Krishna, 2015]. But this solvent driven segregation has not been put forward as a driving force in microfluidic except for the movement of particles [Hajian, 2015].

The production of nanoparticles has been reviewed [Wang, 2015, Ma, 2017, Tao, 2019] and has produced important synthetic success, for example, the reactive precipitation of magnetic particles in co-flow by Abou-Hassan et al [Abou-Hassan, 2009], from whom we have receive the tube microfluidic approach. Other examples are the reactive precipitation of fluorescent perovskite nanoparticle by Lignos et al [Lignos, 2016] and the precipitation of nanometric fluorescent polymeric sensor by A.Reisch [Reisch, 2018]. But few papers have been published on the mechanism of the production of nanoparticles in microfluidics by solvent shifting. The formation of microdroplets through the gathering on nano droplets was postulated [Aubry, 2009]. This is in this community that the focusing of droplets by the Marangoni effect has been first observed [Hajian, 2015].

(40)

The manuscript is organised as following:

Chapter 1 summarises the State of art concerning nucleation, NPLIN, fluorescence imaging (FLIM), and DBDCS molecule.

Chapter 2 describes in detail the Experimental coaxial microfluidic mixer for diffusive

antisolvent precipitation, coupled with a focused IR Laser for NPLIN and a wide-field UV Laser for FLIM. This device will allow a parametric sweep of the different parameters.

Chapter 3 presents the Thermodynamics of water (1)-1,4-dioxane (2)-DBDCS (3)

ternary system used in this work. The molar volume, dynamic viscosity, and refractive indices

of the mixture will be expressed using the Redlich-Kister type equation. After an Introduction to the thermodynamics of antisolvent-solvent-solute ternary mixtures, the Jouyban-Acree equation and the H3M model will be applied to the ternary system of 1-2-3. The thermodynamics of diffusion and its application to the diffusion of 1-2-3 mixture will be discussed. Finally, the thermodynamic stability of 1-2-3 ternary mixture will be addressed.

Chapter 4 exposes the Comsol simulation allowed by the thermodynamic equations developed in the previous chapter. Some preliminary comparisons between predictions and observations are presented.

Chapter 5 exhibits the Part 1 of the Phase diagram of water (1)-1,4-dioxane

(2)-DBDCS (3) system in the coaxial microfluidic mixer: the Non-crystalline phase transition.

After the phenomena observed during the phase transitions by solvent displacement and evidences for antisolvent focusing of DBDCS, a phase diagram of 1-2-3 in the coaxial microfluidic mixer will be established. Then, the soluble region, nano-objects, liquid-liquid phase separation, and kinetic characteristics of the coaxial microflow mixer will be carefully described.

Chapter 6 displays the Part 2 of the Phase diagram of water (1)-1,4-dioxane

(2)-DBDCS (3) system in the coaxial microfluidic mixer: the spontaneous crystallisation. It focuses

(41)

FLIM characterisation of spontaneous crystallisation of DBDCS in microflow: the counting and identifying of flowing fluorescent particles (the crystal size, the birth rate, and the growth rate of spontaneous DBDCS crystals). Finally, a schematic summary of the spontaneous phase transition types observed in the coaxial microfluidic system will be given.

Chapter 7 concerns the Laser-Induce Nucleation in Microfluidics. The effects of the focused IR laser on the different objects produced in Chapter 5 (flows, nanodroplets, nanoparticles, and droplets) and Chapter 6 (crystal production) are described. A complete schematic summary of the NPLIN working phase diagram will be drawn.

The last chapter contains a general discussion and conclusion and emphasises the

(42)

Curriculum research on Sustainable Development Education in Chinese Higher Education -- Education for SD, SD for Education

HAL Id: tel-03276111

https://tel.archives-ouvertes.fr/tel-03276111

Curriculum research on Sustainable Development

Education in Chinese Higher Education – Education for

SD, SD for Education

Tongzhen Zhu

To cite this version:

Laser-induced Nucleation in a

Coaxial Microfluidic Mixer

Thèse de doctorat de l'Université Paris-Saclay

École Normale Supérieure Paris-Saclay

École doctorale n°573 Interfaces : approches interdisciplinaires,

fondements, applications et innovation (Interfaces)

Zhengyu Zhang

LASER-INDUCED NUCLEATION IN A COAXIAL MICROFLUIDIC MIXER

Acknowledgement

To my wife

Weixi Wang Zhang

who gives me the best accompany and solace

Abstract

Résumé

Table of contents

Table of nomenclatures

A

A

B

d

d

d

d

D

F

g

g

G

G



H



H



I

I

J

k

k

k

k

k

K

l

l

L

M

M

n

n

N

N

N

N

N

N

p

Pe

Q

Q

Q



r

r

R

Re

R

S

S



t

t